As bifunctional oxygen evolution/reduction electrocatalysts,transition-metal-based single-atom-doped nitrogen-carbon(NC)matrices are promising successors of the corresponding noblemetal-based catalysts,offering the ad...As bifunctional oxygen evolution/reduction electrocatalysts,transition-metal-based single-atom-doped nitrogen-carbon(NC)matrices are promising successors of the corresponding noblemetal-based catalysts,offering the advantages of ultrahigh atom utilization effciency and surface active energy.However,the fabrication of such matrices(e.g.,well-dispersed single-atom-doped M-N4/NCs)often requires numerous steps and tedious processes.Herein,ultrasonic plasma engineering allows direct carbonization in a precursor solution containing metal phthalocyanine and aniline.When combining with the dispersion effect of ultrasonic waves,we successfully fabricated uniform single-atom M-N4(M=Fe,Co)carbon catalysts with a production rate as high as 10 mg min-1.The Co-N4/NC presented a bifunctional potential drop ofΔE=0.79 V,outperforming the benchmark Pt/C-Ru/C catalyst(ΔE=0.88 V)at the same catalyst loading.Theoretical calculations revealed that Co-N4 was the major active site with superior O2 adsorption-desorption mechanisms.In a practical Zn-air battery test,the air electrode coated with Co-N4/NC exhibited a specific capacity(762.8 mAh g(-1))and power density(101.62 mW cm^(-2)),exceeding those of Pt/C-Ru/C(700.8 mAh g^(-1) and 89.16 mW cm^(-2),respectively)at the same catalyst loading.Moreover,for Co-N4/NC,the potential difference increased from 1.16 to 1.47 V after 100 charge-discharge cycles.The proposed innovative and scalable strategy was concluded to be well suited for the fabrication of single-atom-doped carbons as promising bifunctional oxygen evolution/reduction electrocatalysts for metal-air batteries.展开更多
Rechargeable zinc-air batteries(ZABs)are a promising energy conversion device,which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction(ORR)and oxygen evolution ...Rechargeable zinc-air batteries(ZABs)are a promising energy conversion device,which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction(ORR)and oxygen evolution reactions(OER).Herein,we fabricate a range of bifunctional M-N-C(metal-nitrogen-carbon)catalysts containing M-Nx coordination sites and M/MxC nanoparticles(M=Co,Fe,and Cu)using a new class ofγ-cyclodextrin(CD)based metal-organic framework as the precursor.With the two types of active sites interacting with each other in the catalysts,the obtained Fe@C-FeNC and Co@C-CoNC display superior alkaline ORR activity in terms of low half-wave(E1/2)potential(~0.917 and 0.906 V,respectively),which are higher than Cu@C-CuNC(~0.829 V)and the commercial Pt/C(~0.861 V).As a bifunctional electrocatalyst,the Co@C-CoNC exhibits the best performance,showing a bifunctional ORR/OER overpotential(ΔE)of~0.732 V,which is much lower than that of Fe@C-FeNC(~0.831 V)and Cu@C-CuNC(~1.411 V),as well as most of the robust bifunctional electrocatalysts reported to date.Synchrotron X-ray absorption spectroscopy and density functional theory simulations reveal that the strong electronic correlation between metallic Co nanoparticles and the atomic Co-N4 sites in the Co@C-CoNC catalyst can increase the d-electron density near the Fermi level and thus effectively optimize the adsorption/desorption of intermediates in ORR/OER,resulting in an enhanced bifunctional electrocatalytic performance.The Co@C-CoNC-based rechargeable ZAB exhibited a maximum power density of 162.80 mW cm^(−2) at 270.30 mA cm^(−2),higher than the combination of commercial Pt/C+RuO2(~158.90 mW cm^(−2) at 265.80 mA cm^(−2))catalysts.During the galvanostatic discharge at 10 mA cm^(−2),the ZAB delivered an almost stable discharge voltage of 1.2 V for~140 h,signifying the virtue of excellent bifunctional ORR/OER electrocatalytic activity.展开更多
The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient s...The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.展开更多
Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement.Unlike the previously reported singleatom or dual-atom configura...Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement.Unlike the previously reported singleatom or dual-atom configurations,we designed a new type of binary-atom catalyst,through engineering Fe-N_(4)electronic structure with adjacent Co-N_(2)C_(2)and nitrogen-coordinated Co nanoclusters,as oxygen electrocatalysts.The resultant optimized electronic structure of the Fe-N_(4)active center favors the binding capability of intermediates and enhances oxygen reduction reaction(ORR)activity in both alkaline and acid conditions.In addition,anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge-and mass-transports,and escorts the high bifunctional catalytic activity of the entire catalyst.Further,through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses,the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed.This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior.It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.展开更多
Free-standing and fexible air electrodes with long-lasting bifunctional activities for both the oxygen reduction reaction(ORR)and the oxygen evolution reaction(OER)are crucial to the development of wearable Zn-air rec...Free-standing and fexible air electrodes with long-lasting bifunctional activities for both the oxygen reduction reaction(ORR)and the oxygen evolution reaction(OER)are crucial to the development of wearable Zn-air rechargeable batteries.In this work,we synthesize a fexible air electrode consisting of 3D nanoporous N-doped graphene with trimodal shells and Ni particles through repeated chemical vapor deposition(CVD)and acidic etching processes.Our results indicate that such trimodal graphene morphology significantly enhances the active N-dopant sites and graphene-coated Ni surface,which consequentially boosts both the ORR and OER activities,as well as catalytic durability.First-principles density functional theory(DFT)calculations reveal the synergetic effects between the Ni and the N-doped graphene;namely,the Ni nanoparticles boost the bifunctional activities of the coated N-doped graphene,and in turn the graphene-covering layers enhance the stability of Ni.Thanks to the better protection from the triple graphene shells,our trimodal N-doped graphene/Ni-based Zn-air battery can be stably discharged/recharged beyond 2500 h with low overpotentials.It is reasonable to expect that such freestanding trimodal graphene/Ni would be promising in many fexible energy conversion/storage devices.展开更多
制备具有氧还原(ORR)与氧释放(OER)双功能催化活性的特殊孔道结构电催化剂是锂氧电池研究的挑战之一。本文以氧化石墨烯、硝酸铁、硝酸镧、柠檬酸为原料,结合溶胶凝胶和水热合成方法,制备出还原氧化石墨烯(RGO)与铁酸镧(LaFeO_3)复合的...制备具有氧还原(ORR)与氧释放(OER)双功能催化活性的特殊孔道结构电催化剂是锂氧电池研究的挑战之一。本文以氧化石墨烯、硝酸铁、硝酸镧、柠檬酸为原料,结合溶胶凝胶和水热合成方法,制备出还原氧化石墨烯(RGO)与铁酸镧(LaFeO_3)复合的双功能催化剂(RGO-LaFeO_3)。X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和Raman光谱分析结果确认该复合催化剂由纯相钙钛矿结构LaFeO_3和还原氧化石墨烯组成,扫描电子显微镜(SEM)观察到LaFeO_3纳米颗粒均匀地负载在RGO片层表面。锂氧电池测试结果指出,相对于LaFeO_3纳米粒子(NP-LaFeO_3),RGO-LaFeO_3催化剂具有更好的ORR和OER催化活性,归因于RGO特殊的三维导电多孔结构与LaFeO_3纳米粒子的协同催化作用。以RGO-LaFeO_3作为阴极催化剂的锂氧电池在限1000 m Ah?g^(-1)比容量、100 m A?g^(-1)电流密度条件下,可实现36周稳定的充放电循环,展示出良好的应用前景。展开更多
基金supported by Global Frontier Program through the Global Frontier Hybrid Interface materials(GFHIM)of the National Research Foundation of Korea(NRF)funded by the ministry of science,ICT and Future Planning(2013M3A6B1078874)co-supported by Busan Innovation Institute of Industry,Science&Technology Planning(BISTEP)+1 种基金the financial support of Federal Ministry of Education and Research(BMBF)under the“Make Our Planet Great Again-German Research Initiative”(MOPGAGRI),57429784implemented by the German Academic Exchange Service Deutscher Akademischer Austauschdienst(DAAD)。
文摘As bifunctional oxygen evolution/reduction electrocatalysts,transition-metal-based single-atom-doped nitrogen-carbon(NC)matrices are promising successors of the corresponding noblemetal-based catalysts,offering the advantages of ultrahigh atom utilization effciency and surface active energy.However,the fabrication of such matrices(e.g.,well-dispersed single-atom-doped M-N4/NCs)often requires numerous steps and tedious processes.Herein,ultrasonic plasma engineering allows direct carbonization in a precursor solution containing metal phthalocyanine and aniline.When combining with the dispersion effect of ultrasonic waves,we successfully fabricated uniform single-atom M-N4(M=Fe,Co)carbon catalysts with a production rate as high as 10 mg min-1.The Co-N4/NC presented a bifunctional potential drop ofΔE=0.79 V,outperforming the benchmark Pt/C-Ru/C catalyst(ΔE=0.88 V)at the same catalyst loading.Theoretical calculations revealed that Co-N4 was the major active site with superior O2 adsorption-desorption mechanisms.In a practical Zn-air battery test,the air electrode coated with Co-N4/NC exhibited a specific capacity(762.8 mAh g(-1))and power density(101.62 mW cm^(-2)),exceeding those of Pt/C-Ru/C(700.8 mAh g^(-1) and 89.16 mW cm^(-2),respectively)at the same catalyst loading.Moreover,for Co-N4/NC,the potential difference increased from 1.16 to 1.47 V after 100 charge-discharge cycles.The proposed innovative and scalable strategy was concluded to be well suited for the fabrication of single-atom-doped carbons as promising bifunctional oxygen evolution/reduction electrocatalysts for metal-air batteries.
基金supported by the Shenzhen Government’s Plan of Science and Technology(JCYJ20190808121407676 and 20200813142301001)National Natural Science Foundation of China(22178223 and 22262010)+1 种基金Guangxi Science and Technology Fund for Distinguished High-Talent Introduction Program(No.RZ2200002233AC22035091).
文摘Rechargeable zinc-air batteries(ZABs)are a promising energy conversion device,which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction(ORR)and oxygen evolution reactions(OER).Herein,we fabricate a range of bifunctional M-N-C(metal-nitrogen-carbon)catalysts containing M-Nx coordination sites and M/MxC nanoparticles(M=Co,Fe,and Cu)using a new class ofγ-cyclodextrin(CD)based metal-organic framework as the precursor.With the two types of active sites interacting with each other in the catalysts,the obtained Fe@C-FeNC and Co@C-CoNC display superior alkaline ORR activity in terms of low half-wave(E1/2)potential(~0.917 and 0.906 V,respectively),which are higher than Cu@C-CuNC(~0.829 V)and the commercial Pt/C(~0.861 V).As a bifunctional electrocatalyst,the Co@C-CoNC exhibits the best performance,showing a bifunctional ORR/OER overpotential(ΔE)of~0.732 V,which is much lower than that of Fe@C-FeNC(~0.831 V)and Cu@C-CuNC(~1.411 V),as well as most of the robust bifunctional electrocatalysts reported to date.Synchrotron X-ray absorption spectroscopy and density functional theory simulations reveal that the strong electronic correlation between metallic Co nanoparticles and the atomic Co-N4 sites in the Co@C-CoNC catalyst can increase the d-electron density near the Fermi level and thus effectively optimize the adsorption/desorption of intermediates in ORR/OER,resulting in an enhanced bifunctional electrocatalytic performance.The Co@C-CoNC-based rechargeable ZAB exhibited a maximum power density of 162.80 mW cm^(−2) at 270.30 mA cm^(−2),higher than the combination of commercial Pt/C+RuO2(~158.90 mW cm^(−2) at 265.80 mA cm^(−2))catalysts.During the galvanostatic discharge at 10 mA cm^(−2),the ZAB delivered an almost stable discharge voltage of 1.2 V for~140 h,signifying the virtue of excellent bifunctional ORR/OER electrocatalytic activity.
基金supported by the Beijing Natural Science Foundation (2222004)。
文摘The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.
基金funded by the National Natural Science Foundation of China (22208331, 52003300)the Natural Sciences and Engineering Research Council of Canada (NSERC)+4 种基金the Fonds de Recherche du Québec-Nature et Technologies (FRQNT)Centre Québécois sur les Materiaux Fonctionnels (CQMF), McGill Universityécole de Technologie Supérieure (éTS)Institut National de la Recherche Scientifique (INRS)the support from the Marcelle-Gauvreau Engineering Research Chair program
文摘Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement.Unlike the previously reported singleatom or dual-atom configurations,we designed a new type of binary-atom catalyst,through engineering Fe-N_(4)electronic structure with adjacent Co-N_(2)C_(2)and nitrogen-coordinated Co nanoclusters,as oxygen electrocatalysts.The resultant optimized electronic structure of the Fe-N_(4)active center favors the binding capability of intermediates and enhances oxygen reduction reaction(ORR)activity in both alkaline and acid conditions.In addition,anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge-and mass-transports,and escorts the high bifunctional catalytic activity of the entire catalyst.Further,through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses,the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed.This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior.It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.
基金financially supported by the Development and Reform Commission of Shenzhen Municipalitythe National Natural Science Foundation of China(Grant Nos.51702031,51871077)+1 种基金the Shenzhen Fundamental Research Program(Grant Nos.JCYJ20180306171644942,JCYJ20180507184623297,KQJSCX20180328165656256)the Innovation Project from Harbin Institute of Technology。
文摘Free-standing and fexible air electrodes with long-lasting bifunctional activities for both the oxygen reduction reaction(ORR)and the oxygen evolution reaction(OER)are crucial to the development of wearable Zn-air rechargeable batteries.In this work,we synthesize a fexible air electrode consisting of 3D nanoporous N-doped graphene with trimodal shells and Ni particles through repeated chemical vapor deposition(CVD)and acidic etching processes.Our results indicate that such trimodal graphene morphology significantly enhances the active N-dopant sites and graphene-coated Ni surface,which consequentially boosts both the ORR and OER activities,as well as catalytic durability.First-principles density functional theory(DFT)calculations reveal the synergetic effects between the Ni and the N-doped graphene;namely,the Ni nanoparticles boost the bifunctional activities of the coated N-doped graphene,and in turn the graphene-covering layers enhance the stability of Ni.Thanks to the better protection from the triple graphene shells,our trimodal N-doped graphene/Ni-based Zn-air battery can be stably discharged/recharged beyond 2500 h with low overpotentials.It is reasonable to expect that such freestanding trimodal graphene/Ni would be promising in many fexible energy conversion/storage devices.
文摘制备具有氧还原(ORR)与氧释放(OER)双功能催化活性的特殊孔道结构电催化剂是锂氧电池研究的挑战之一。本文以氧化石墨烯、硝酸铁、硝酸镧、柠檬酸为原料,结合溶胶凝胶和水热合成方法,制备出还原氧化石墨烯(RGO)与铁酸镧(LaFeO_3)复合的双功能催化剂(RGO-LaFeO_3)。X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和Raman光谱分析结果确认该复合催化剂由纯相钙钛矿结构LaFeO_3和还原氧化石墨烯组成,扫描电子显微镜(SEM)观察到LaFeO_3纳米颗粒均匀地负载在RGO片层表面。锂氧电池测试结果指出,相对于LaFeO_3纳米粒子(NP-LaFeO_3),RGO-LaFeO_3催化剂具有更好的ORR和OER催化活性,归因于RGO特殊的三维导电多孔结构与LaFeO_3纳米粒子的协同催化作用。以RGO-LaFeO_3作为阴极催化剂的锂氧电池在限1000 m Ah?g^(-1)比容量、100 m A?g^(-1)电流密度条件下,可实现36周稳定的充放电循环,展示出良好的应用前景。
